Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
  • C10M171/008—Lubricant compositions compatible with refrigerants
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
  • C10M105/38—Esters of polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
  • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/106—Carbon dioxide
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/122—Halogenated hydrocarbons
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/22—All components of a mixture being fluoro compounds
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
  • C10M2207/2835—Esters of polyhydroxy compounds used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
  • C10M2207/3025—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
  • C10M2207/3045—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/09—Characteristics associated with water
  • C10N2020/097—Refrigerants
  • C10N2020/101—Containing Hydrofluorocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/09—Characteristics associated with water
  • C10N2020/097—Refrigerants
  • C10N2020/106—Containing Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present invention relates to a working fluid composition for a refrigerator and a refrigerator oil.
• the “refrigerator” in the present invention includes an automobile air conditioner, a dehumidifier, a refrigerator, a refrigerator / freezer warehouse, a vending machine, a showcase, a cooling device in a chemical plant, a residential air conditioner, a packaged air conditioner, a hot water supply. Heat pumps and the like are included.
• R134a 1,1,1,2-tetrafluoroethane
• HFC hydrofluorocarbon
• R410A which is a mixed refrigerant whose mass ratio of methane (R32) and pentafluoroethane (R125) is 1/1, is widely used.
• Patent Document 1 discloses an ester synthesized from trimethylolpropane and / or neopentyl glycol, a specific dibasic acid, and a monohydric alcohol or a monohydric fatty acid as R32 refrigerant refrigerant oil. Further, in Patent Document 2, a fatty acid containing 20 to 60% by mass of monobasic fatty acid having a carbon number of 5 or less for R32 single or R32 containing 50% by mass or more and having a carbon number greater than 8 Discloses an ester refrigerating machine oil using a branched fatty acid and having a viscosity at 40 ° C. of 32 to 100 cst.
• Patent Document 3 discloses an alcohol component containing 90% by mass or more of trimethylolpropane, a monovalent fatty acid having 8 to 12 carbon atoms and adipic acid, and capryl.
• a lubrication comprising a synthetic ester obtained by reacting a monovalent fatty acid having 8 to 12 carbon atoms containing 90% by mass or more of acid and / or capric acid and a carboxylic acid component containing 90% by mass or more of adipic acid in total.
• An oil base oil is disclosed.
• the present invention has been made in view of the above problems, and can maintain a thick oil film even under severe lubrication conditions caused by the refrigerant coexisting and dissolving in the refrigerating machine oil, has a large wear resistance effect, and is stable.
• An object is to provide an excellent working fluid composition for a refrigerator and a refrigerator oil.
• the present inventors are a complex ester synthesized from a specific polyhydric alcohol, a polybasic acid, a monohydric alcohol or a monohydric fatty acid, and a polyol synthesized from a specific polyhydric alcohol and a monohydric fatty acid. It has been found that a working fluid containing a refrigerating machine oil based on an ester blended with an ester and a predetermined refrigerant can achieve both wear resistance and stability, and has completed the present invention.
• the present invention provides a working fluid composition for a refrigerator as described in [1] to [6] below and a refrigerator oil as described in [7] below.
• A a polyhydric alcohol containing at least one selected from neopentyl glycol, trimethylolpropane and pentaerythritol, at least one selected from polybasic acids having 6 to 12 carbon atoms, and 4 to 4 carbon atoms A complex ester synthesized from 18 monohydric alcohols and at least one monovalent fatty acid selected from 4 to 18 carbon atoms, and (B) selected from neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol.
• the (B) polyol ester is an ester synthesized from at least one selected from neopentyl glycol and pentaerythritol and at least one selected from monovalent fatty acids having 4 to 9 carbon atoms.
• the polyol ester is an ester synthesized from pentaerythritol and a mixed fatty acid of a branched fatty acid having 4 carbon atoms and 3,5,5-trimethylhexanoic acid, according to [1] to [6]
• the working fluid composition for refrigerators as described in any one.
• a working fluid composition for a refrigerator that can maintain a thick oil film even under severe lubrication conditions caused by the refrigerant coexisting and dissolving in the refrigerator oil, has a large wear resistance effect, and has excellent stability.
• Refrigerating machine oil can be provided.
• the refrigerating machine oil is (A) a polyhydric alcohol containing at least one selected from neopentyl glycol, trimethylolpropane and pentaerythritol, at least one selected from polybasic acids having 6 to 12 carbon atoms, and one having 4 to 18 carbon atoms A complex ester synthesized from at least one selected from a monohydric alcohol and a monovalent fatty acid having 4 to 18 carbon atoms, and (B) A polyol synthesized from at least one polyhydric alcohol selected from neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol and at least one selected from monovalent fatty acids having 4 to 18 carbon atoms.
• a mixed ester prepared by mixing an ester at a mass ratio of (A) complex ester / (B) polyol ester of 5/95 to 95/5 as a base oil; Carbon dioxide, 1,1,1,2-tetrafluoroethane, a mixture of difluoromethane and pentafluoroethane, a mixture of difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane, and pentafluoro Used with a refrigerant selected from a mixture of ethane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane.
• the working fluid composition for a refrigerator is (A) a polyhydric alcohol containing at least one selected from neopentyl glycol, trimethylolpropane and pentaerythritol, at least one selected from polybasic acids having 6 to 12 carbon atoms, and one having 4 to 18 carbon atoms A complex ester synthesized from at least one selected from a monohydric alcohol and a monovalent fatty acid having 4 to 18 carbon atoms, and (B) at least one selected from neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol A polyol ester synthesized from one kind of polyhydric alcohol and at least one kind selected from monovalent fatty acids having 4 to 18 carbon atoms is converted into a mass ratio of (A) complex ester / (B) polyol ester of 5/95 to 95.
• the working fluid composition for a refrigerator according to the present embodiment includes the refrigerating machine oil according to the present embodiment, carbon dioxide, 1,1,1,2-tetrafluoroethane, a mixture of difluoromethane and pentafluoroethane, difluoro Mixtures of methane, pentafluoroethane and 1,1,1,2-tetrafluoroethane, and mixtures of pentafluoroethane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane
• coolant chosen from is included.
• the above complex ester is less soluble in the refrigerant than conventional refrigeration oil, and thus has a low compatibility with the refrigerant, but can maintain a thick oil film.
• said polyol ester has favorable compatibility with a refrigerant
• the complex ester has a high molecular weight and therefore has a high viscosity. Therefore, the complex ester is hardly compatible with the refrigerant, and is not suitable for use alone as a base oil for refrigerating machine oil that needs compatibility with the refrigerant from the viewpoint of oil return to the compressor.
• One of the features of this embodiment is that the properties can be balanced by mixing the complex ester with an oil having good compatibility with the refrigerant, such as the above polyol ester.
• Complex esters preferably 20 mm 2 / s or more, more preferably 40 mm 2 / s or more, more preferably at 50 mm 2 / s or more, preferably not more than 500 mm 2 / s, more preferably 400mm 2 / s or less, more preferably 200 mm 2 / s or less, and particularly preferably 90 mm 2 / s or less.
• Complex esters preferably 5 mm 2 / s or more, more preferably 6 mm 2 / s or more, more preferably at 7 mm 2 / s or more, preferably not more than 30 mm 2 / s, more preferably 20mm 2 / s or less, more preferably 15 mm 2 / s or less.
• the viscosity index of the complex ester is preferably 100 or more, more preferably 115 or more, and preferably 180 or less.
• the kinematic viscosity and viscosity index in the present invention mean kinematic viscosity and viscosity index measured in accordance with JIS K2283, respectively.
• the complex ester obtained by the method (b) is slightly inferior in stability to the complex ester obtained by the method (a) because a relatively strong acid is generated when hydrolyzed during use as a refrigerating machine oil. There is a tendency.
• a complex ester obtained by the method (a) having higher stability is preferable.
• the polyhydric alcohol constituting the complex ester at least one selected from neopentyl glycol, trimethylolpropane and pentaerythritol is used.
• neopentyl glycol and trimethylolpropane are preferable in order to ensure a suitable viscosity as a base oil and to obtain good low temperature characteristics.
• neopentyl glycol is more preferable because the viscosity can be adjusted widely.
• the polyhydric alcohol constituting the complex ester is a carbon other than neopentyl glycol because it can further improve lubricity. It is preferable to further contain a dihydric alcohol having a number of 2 to 10. Examples of the dihydric alcohol having 2 to 10 carbon atoms other than neopentyl glycol include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5.
• butanediol having a well-balanced characteristic of the synthesized base oil is preferable.
• examples of butanediol include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and the like.
• 1,3-butanediol and 1,4-butanediol are more preferable from the viewpoint of obtaining good characteristics.
• the dihydric alcohol having 2 to 10 carbon atoms other than neopentyl glycol is preferably 1.2 mol or less, more preferably 0 with respect to 1 mol of polyhydric alcohol selected from neopentyl glycol, trimethylolpropane and pentaerythritol. .8 mol or less, more preferably 0.4 mol or less.
• the polybasic acid constituting the complex ester is at least one selected from polybasic acids having 6 to 12 carbon atoms.
• polybasic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, trimellitic acid and the like.
• adipic acid and sebacic acid are preferable, and adipic acid is more preferable in terms of excellent balance of properties of the synthesized ester and easy availability.
• This polybasic acid is preferably 0.4 mol or more, more preferably 0.5 mol or more, still more preferably 0.00 mol, per mol of polyhydric alcohol selected from neopentyl glycol, trimethylolpropane and pentaerythritol. It is used in an amount of 6 mol or more, preferably 4 mol or less, more preferably 3 mol or less, still more preferably 2.5 mol or less.
• the carboxyl group has 4 to 4 carbon atoms. Esterification is performed with at least one selected from 18 monohydric alcohols.
• Examples of the monohydric alcohol having 4 to 18 carbon atoms include linear or branched butanol, linear or branched pentanol, linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear Alternatively, aliphatic alcohols such as branched nonanol, linear or branched decanol, linear or branched dodecanol, and oleyl alcohol can be used.
• the monohydric alcohol having 4 to 18 carbon atoms is preferably a monohydric alcohol having 6 to 10 carbon atoms, and more preferably a monohydric alcohol having 8 to 10 carbon atoms from the viewpoint of balance of characteristics. Among these, 2-ethylhexanol and 3,5,5-trimethylhexanol are more preferable from the viewpoint that the synthesized complex ester has good low-temperature characteristics.
• the hydroxyl group has 4 to 18 carbon atoms. It is esterified with at least one selected from monovalent fatty acids.
• Examples of the monovalent fatty acid having 4 to 18 carbon atoms include linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptanoic acid, linear or branched octane Examples thereof include acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched dodecanoic acid, and oleic acid.
• the monovalent fatty acid having 4 to 18 carbon atoms is preferably a monovalent fatty acid having 8 to 10 carbon atoms, and more preferably 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid from the viewpoint of low temperature characteristics. It is.
• the polyol ester in this embodiment includes at least one polyhydric alcohol selected from neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol, and at least one selected from monovalent fatty acids having 4 to 18 carbon atoms. It is a polyol ester synthesized from
• polyhydric alcohol constituting the polyol ester trimethylolpropane and pentaerythritol are preferable, and pentaerythritol is more preferable from the viewpoint of balance of characteristics.
• Examples of the monovalent fatty acid having 4 to 18 carbon atoms constituting the polyol ester include linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptanoic acid, direct Examples include chain or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched dodecanoic acid, and oleic acid.
• the monovalent fatty acid having 4 to 18 carbon atoms is preferably a monovalent fatty acid having 4 to 9 carbon atoms from the viewpoint of low temperature characteristics, more preferably branched butanoic acid, branched pentanoic acid, branched hexanoic acid, Branched heptanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.
• the polyol ester according to this embodiment is preferably a polyol ester of pentaerythritol and two or more mixed fatty acids selected from branched fatty acids having 4 to 9 carbon atoms from the viewpoint of compatibility with the refrigerant.
• a polyol ester of a mixed fatty acid of a branched fatty acid of number 4 and a branched fatty acid of carbon number 9 is more preferable, and a polyol ester of a mixed fatty acid of pentaerythritol, a branched fatty acid of carbon number 4 and 3,5,5-trimethylhexanoic acid is preferable. Further preferred.
• Kinematic viscosity at 40 ° C. of the polyol ester is preferably 5 mm 2 / s or more, more preferably 20 mm 2 / s or more, more preferably at 30 mm 2 / s or more, preferably not more than 300 mm 2 / s, more preferably 200mm 2 / s or less, more preferably 60 mm 2 / s.
• the viscosity index of the polyol ester is preferably 70 or more, more preferably 80 or more, still more preferably 90, and preferably 150 or less.
• the mass ratio (content of (A) / content of (B)) between the content of (A) complex ester and the content of (B) polyol ester is 5 /
• it is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30.
• the pour point of the refrigerating machine oil is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
• the pour point in the present invention means a pour point measured according to JIS K2269.
• the acid value of the refrigerating machine oil is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH in order to prevent corrosion of the metal used in the refrigerating machine or piping and to suppress deterioration of the refrigerating machine oil itself. / G or less.
• the acid value in the present invention means an acid value measured according to JIS K2501 “Acid Value Test Method”.
• the flash point of the refrigerating machine oil is preferably 120 ° C. or higher, more preferably 200 ° C. or higher.
• the flash point in the present invention means a flash point measured according to JIS K2265-4.
• the water content of the refrigerating machine oil is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
• the moisture content is required to be low from the viewpoint of stability of the refrigerator oil and electrical insulation.
• the refrigerating machine oil may further contain other base oils such as a mineral base oil and a synthetic base oil in addition to the above complex ester and polyol ester.
• the total of the content of the complex ester and the content of the polyol ester is preferably 80% by mass or more and more preferably 95% by mass or more based on the total amount of the refrigerating machine oil.
• Refrigerating machine oil can contain various additives in order to further improve the wear resistance.
• Suitable additives include phosphate esters.
• phosphate esters triphenyl phosphate (TPP) and tricresyl phosphate (TCP) are preferable.
• Suitable sulfur-based additives include sulfide compounds. Although there are various types of sulfide compounds, monosulfide compounds are preferable from the viewpoints of ensuring the stability of the refrigerating machine oil and suppressing the deterioration of copper frequently used in the refrigeration equipment.
• the refrigerating machine oil may contain various additives conventionally used in lubricating oils in addition to the above-mentioned additives in order to further improve the performance as long as the object of the present invention is not impaired.
• additives include antioxidants, friction modifiers, antiwear agents, extreme pressure agents, rust inhibitors, metal deactivators, and antifoaming agents.
• the refrigerating machine oil preferably contains 0.02% by mass or more, and preferably 0.5% by mass or less of the phenolic compound as an antioxidant based on the total amount of the refrigerating machine oil.
• Examples of the friction modifier include aliphatic amines, aliphatic amides, aliphatic imides, alcohols, esters, phosphate ester amine salts, phosphite ester amine salts, and the like.
• Examples of the antiwear agent include zinc dialkyldithiophosphate.
• Examples of extreme pressure agents include sulfurized olefins and sulfurized fats and oils.
• Examples of the rust preventive agent include esters or partial esters of alkenyl succinic acid.
• Examples of the metal deactivator include benzotriazole and benzotriazole derivatives.
• Examples of antifoaming agents include silicone compounds and polyester compounds.
• the refrigerant used together with the refrigerating machine oil according to the present embodiment and the refrigerant contained in the working fluid composition for the refrigerating machine according to the present embodiment are carbon dioxide, 1,1,1,2-tetrafluoroethane (R134a), difluoro Mixture of methane (R32) and pentafluoroethane (R125), mixture of difluoromethane (R32), pentafluoroethane (R125) and 1,1,1,2-tetrafluoroethane (R134a), and pentafluoroethane It is selected from a mixture of (R125), 1,1,1,2-tetrafluoroethane (R134a) and 1,1,1-trifluoroethane (R143a).
• Such a refrigerant may be one selected from the above or two or more. In addition to the refrigerant selected from the above, other refrigerants may be used in combination.
• the content of the refrigerant selected from the above is preferably 60 to 100% by mass, and more preferably 80 to 100% by mass based on the total amount of the refrigerant.
• the mass ratio (R32 / R125) can be set to 40 to 70/60 to 30, for example.
• a mixture having a mass ratio (R32 / R125) of 60/40, a mixture of 50/50 (R410A), and a mixture of 45/55 (R410B) are preferably used.
• the mass ratio (R32 / R125 / R134a) is, for example, 15 to 35 / It can be 5-40 / 40-70.
• the mixture whose mass ratio (R32 / R125 / R134a) is 30/10/60, the mixture (R407C) which is 23/25/52, and the mixture (R407E) which is 25/15/60 are preferably used. It is done.
• the mass ratio (R125 / R134a / R143a) can be, for example, 35 to 55/1 to 15/40 to 60.
• a mixture (R404A) having a mass ratio (R125 / R134a / R143a) of 44/4/52 is preferably used.
• the content of the refrigerating machine oil in the working fluid composition for a refrigerating machine is not particularly limited, but is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 500 parts by mass with respect to 100 parts by mass of the refrigerant. Hereinafter, it is more preferably 400 parts by mass or less.
• base oils 1 to 8 having the compositions shown in Tables 1 and 2 were prepared using the following base materials.
• [A] Complex ester (A1) An ester intermediate obtained by reacting neopentyl glycol (1 mol) and 1,4-butanediol (0.3 mol) with adipic acid (2.4 mol), An ester obtained by reacting 5,5-trimethylhexanol (2.5 mol) and removing the remaining unreacted product by distillation (kinematic viscosity at 40 ° C. 67.8 mm 2 / s, kinematic viscosity at 100 ° C. 10. 6 mm 2 / s, viscosity index 145).
• [C] hydrocarbon oil C1 poly ⁇ - olefin (PAO) (kinematic viscosity at kinematic viscosity 34.0mm 2 / s, 100 °C at 40 °C 6.9mm 2 / s, viscosity index 168)
• C2 Poly ⁇ -olefin (PAO) (kinematic viscosity at 40 ° C. 68.0 mm 2 / s, kinematic viscosity at 100 ° C. 9.9 mm 2 / s, viscosity index 128)
• R407C Difluoromethane / pentafluoroethane / 1,1,1,2-tetrafluoroethane mixture (mass ratio 23/25/52) CO 2 : Carbon dioxide
• R404A Mixture of pentafluoroethane / 1,1,1,2-tetrafluoroethane / 1,1,1-trifluoroethane (mass ratio 44/4/52)
• R134a 1,1,1,2-tetrafluoroethane
• R410A Difluoromethane / pentafluoroethane mixture (mass ratio 50/50)
• a wear resistance test was performed using a high-pressure atmosphere friction tester (rotating sliding method of rotating vane material and fixed disk material) manufactured by Shinko Machine Co., Ltd., which can create a refrigerant atmosphere similar to that of an actual compressor.
• the test conditions were one of the following abrasion resistance tests (1) to (5) for each type of refrigerant evaluated.
• Abrasion resistance test-In all of (1) to (5) the conditions of oil amount 600 ml, test temperature 110 ° C., rotation speed 500 rpm, load load 80 kgf, test time 1 hour are common. It is common to use SKH-51 as the vane material and FC250 as the disk material. The wear resistance was evaluated based on the wear depth of the vane material because the amount of wear of the disk material was extremely small. The results obtained are shown in Tables 3-17.
• the stability test was conducted in accordance with JIS K2211-09 (autoclave test), and 80 g of sample oil whose water content was adjusted to 100 ppm was weighed into an autoclave, and the catalyst (iron, copper, and aluminum wires, each having an outer diameter of 1 .6 mm ⁇ length 50 mm) and 20 g of the evaluation refrigerant were sealed, heated to 150 ° C., and the appearance and acid value (JIS C2101) of the sample oil after 150 hours were measured. The results obtained are shown in Tables 3-17.
• the working fluid composition for refrigerating machine and the refrigerating machine oil according to the present invention are excellent in wear resistance even under severe lubricating conditions, and thus have a remarkable effect of greatly improving lubricity. Therefore, a refrigeration / air-conditioning system with high cooling efficiency that has a compressor, a condenser, a throttling device, an evaporator, etc., and circulates a refrigerant between them, especially a rotary type, a swing type, a scroll type, etc. It can be suitably used in the system and is useful in the fields of room air conditioners, packaged air conditioners, refrigerators, car air conditioners, industrial refrigerators, and the like.

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